JP6890477B2 - Hydrogen generating material manufacturing method, fuel cell, hydrogen generating method - Google Patents

Hydrogen generating material manufacturing method, fuel cell, hydrogen generating method Download PDF

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JP6890477B2
JP6890477B2 JP2017116358A JP2017116358A JP6890477B2 JP 6890477 B2 JP6890477 B2 JP 6890477B2 JP 2017116358 A JP2017116358 A JP 2017116358A JP 2017116358 A JP2017116358 A JP 2017116358A JP 6890477 B2 JP6890477 B2 JP 6890477B2
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mass
hydrogen
film
thermal spraying
aluminum
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JP2019001674A (en
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正 森田
正 森田
中村　亮太
亮太 中村
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Ulvac Inc
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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Description

本発明は水素を発生させる技術に係り、特に、燃料電池用の水素を発生させる技術に関する。 The present invention relates to a technique for generating hydrogen, and more particularly to a technique for generating hydrogen for a fuel cell.

化石燃料の消費による地球温暖化や、エネルギー資源の逼迫の中で、水素をエネルギーとする燃料電池は注目されている。
燃料電池は、家庭用、産業用、自動車用、携帯機器用電源としての用途が考えられているが、特に、使いきりではなく、また、充電などに要する時間なども必要がなく、水素を発生させる材料を補充することで発電が可能になることから、長時間の運転に対応できる電池としての可能性は高いと言われている。
しかしながら水素発生材料の安全性や可搬性には改良すべき点があり、取り扱いが簡単で発電が容易な水素発生材料が求められている。 Amid global warming caused by fossil fuel consumption and tight energy resources, fuel cells that use hydrogen as energy are drawing attention.
Fuel cells are considered to be used as power sources for households, industries, automobiles, and mobile devices, but in particular, they are not used up and do not require time for charging, etc., and generate hydrogen. It is said that there is a high possibility as a battery that can handle long-term operation because it is possible to generate electricity by replenishing the material to be used.
However, there are points to be improved in the safety and portability of hydrogen-generating materials, and there is a demand for hydrogen-generating materials that are easy to handle and generate electricity.

特開昭６３−２７０４５９号公報Japanese Unexamined Patent Publication No. 63-270459 特開２０００−２３９８３７号公報Japanese Unexamined Patent Publication No. 2000-239837 特開２００５−２５６０６３号公報JP-A-2005-25663 ＷＯ２０１２／０２６３４９号公報WO2012 / 026349 特開２０１３−１４０９５０号公報Japanese Unexamined Patent Publication No. 2013-140950

保存・運搬・取り扱いに容易な水素発生材料を提供することにある。 The purpose is to provide hydrogen generating materials that are easy to store, transport, and handle.

上記課題を解決するために、本発明は、水素発生材料片と水とを反応させて水素を生成し、生成された水素と酸素を反応させて発電し、負荷に電力を供給する燃料電池の水素を発生させる燃料電池の前記水素発生材料片を製造する水素発生材料製造方法であって、添加金属とアルミニウムとが混合された溶射原料を成形して所定形状の溶射材料を得る成形工程と、前記溶射材料を熔融させて熔融物の溶滴を吹き飛ばして成膜用基板の成膜面に付着させて溶射膜を形成する溶射工程と、前記溶射膜を前記成膜面から剥離させ、前記溶射膜から所望形状の水素発生材料片を形成する片形成工程と、を有し、前記添加金属は、Ｓｎ、Ｉｎ又はＢｉのいずれか一種又は複数種から成り、アルミニウム１００質量％に対して０．１質量％以上２０質量％以下の範囲で含有させる水素発生材料製造方法である。
また、本発明は、前記溶射工程の後、前記溶射膜を圧延して薄くする圧延工程が設けられた水素発生材料製造方法である。
また、本発明は、前記溶射原料には前記アルミニウム１００質量％に対してＳｉを０．２質量％以上０．５質量％以下の範囲で含有させた、水素発生材料製造方法である。
また、本発明は、前記溶射原料には前記アルミニウム１００質量％に対して、Ｍｇを０．２質量％以上２質量％以下の範囲で含有させた、水素発生材料製造方法である。
また、本発明は、前記添加金属はＢｉを含有し、前記溶射原料には前記アルミニウム１００質量％に対して０．２質量％以上２質量％以下の範囲でＭｇを含有させ、前記溶射膜又は前記水素発生材料片の少なくとも一方を熱処理する水素発生材料製造方法である。
また、本発明は、水素を発生させる水素発生装置と、水素と酸素を反応させて発電し、負荷に電力を供給する電池本体と、を有する燃料電池であって、前記水素発生装置は、水と水素発生材料片とを反応させ、水素を発生させて前記電池本体に供給する反応容器と、を有し、前記水素発生材料片は、添加金属とアルミニウムとが混合された溶射原料が熔融されて生成された溶滴が吹き飛ばされて成膜用基板の成膜面に付着して形成された溶射膜から形成され、前記添加金属は、Ｓｎ、Ｉｎ又はＢｉのいずれか一種又は複数種から成り、アルミニウム１００質量％に対して０．１質量％以上２０質量％以下の範囲で含有された燃料電池である。
また、本発明は、前記溶射原料には前記アルミニウム１００質量％に対してＳｉを０．２質量％以上０．５質量％以下の範囲で含有された、燃料電池である。
また、本発明は、前記溶射原料には前記アルミニウム１００質量％に対して、Ｍｇが０．２質量％以上２質量％以下の範囲で含有された燃料電池である。
また、本発明は、前記添加金属はＢｉを含有し、前記溶射原料には前記アルミニウム１００質量％に対して０．２質量％以上２質量％以下の範囲でＭｇが含有され、前記溶射膜又は前記水素発生材料片は熱処理がされた燃料電池である。
また、本発明は、水素発生材料片と水とを反応容器内で反応させて水素を生成し、生成された水素と酸素を反応させて発電し、負荷に電力を供給する燃料電池の前記反応容器内で水素を発生させる水素発生方法であって、添加金属とアルミニウムとが混合された溶射原料を成形して所定形状の溶射材料を得る成形工程と、前記溶射材料を熔融させて溶滴を生成し、前記溶滴を吹き飛ばして成膜用基板の成膜面に付着させて溶射膜を形成する溶射工程と、前記溶射膜を前記成膜面から剥離させた後、前記溶射膜から所望形状の水素発生材料片を形成する切断工程と、前記水素発生材料片と水とを前記反応容器内で接触させ、反応によって水素を発生させる水素発生工程と、を有し、前記添加金属は、Ｓｎ、Ｉｎ又はＢｉのいずれか一種又は複数種から成り、アルミニウム１００質量％に対して０．１質量％以上２０質量％以下の範囲で含有させる水素発生方法である。
また、本発明は、前記溶射工程の後、前記切断工程の前に、前記溶射膜を圧延して薄くする圧延工程が設けられた水素発生方法である。
また、本発明は、前記溶射原料には前記アルミニウム１００質量％に対してＳｉを０．２質量％以上０．５質量％以下の範囲で含有させた、水素発生方法である。
また、本発明は、前記溶射原料には前記アルミニウム１００質量％に対して、Ｍｇを０．２質量％以上２質量％以下の範囲で含有させた、水素発生方法である。
また、本発明は、前記添加金属はＢｉを含有し、前記溶射原料には前記アルミニウム１００質量％に対して０．２質量％以上２質量％以下の範囲でＭｇを含有させ、前記溶射膜又は前記水素発生材料片を熱処理する水素発生方法である。
また、本発明は、Ｓｎ、Ｉｎ又はＢｉのいずれか一種又は複数種から成る添加金属が、アルミニウム１００質量％に対して０．１質量％以上２０質量％以下の範囲で含有され、前記添加金属が前記アルミニウム中に分散された構造を有する水素発生材料である。
また、本発明は、前記アルミニウム１００質量％に対してＳｉを０．２質量％以上０．５質量％以下の範囲で含有する水素発生材料である。
また、本発明は、前記アルミニウム１００質量％に対してＭｇを０．２質量％以上２質量％以下の範囲で含有する水素発生材料である。
また、本発明は、前記添加金属はＢｉを含有し、前記アルミニウム１００質量％に対して０．２質量％以上２質量％以下の範囲でＭｇを含有し、熱処理がされた水素発生材料である。 In order to solve the above problems, the present invention relates to a fuel cell that reacts a hydrogen generating material piece with water to generate hydrogen, reacts the generated hydrogen with oxygen to generate power, and supplies power to a load. A method for producing a hydrogen-generating material for producing the hydrogen-generating material piece of a fuel cell for generating hydrogen, which comprises molding a spraying raw material in which an additive metal and aluminum are mixed to obtain a spraying material having a predetermined shape. A spraying step of melting the sprayed material to blow off droplets of the molten material and adhering it to the film-forming surface of the film-forming substrate to form a sprayed film, and a spraying step of peeling the sprayed film from the film-forming surface and spraying the film. It has a piece forming step of forming a hydrogen generating material piece having a desired shape from a film, and the additive metal is composed of any one or more of Sn, In or Bi, and is 0. This is a method for producing a hydrogen generating material, which contains 1% by mass or more and 20% by mass or less.
Further, the present invention is a method for producing a hydrogen generating material, which is provided with a rolling step of rolling and thinning the sprayed film after the spraying step.
Further, the present invention is a method for producing a hydrogen generating material in which Si is contained in the range of 0.2% by mass or more and 0.5% by mass or less with respect to 100% by mass of the aluminum in the thermal spraying raw material.
Further, the present invention is a method for producing a hydrogen generating material, in which Mg is contained in the range of 0.2% by mass or more and 2% by mass or less with respect to 100% by mass of the aluminum in the thermal spraying raw material.
Further, in the present invention, the additive metal contains Bi, and the thermal spraying raw material contains Mg in a range of 0.2% by mass or more and 2% by mass or less with respect to 100% by mass of the aluminum, and the thermal spraying film or This is a method for producing a hydrogen generating material, in which at least one of the hydrogen generating material pieces is heat-treated.
Further, the present invention is a fuel cell having a hydrogen generator that generates hydrogen and a battery body that reacts hydrogen and oxygen to generate power and supplies power to a load, and the hydrogen generator is water. It has a reaction vessel that reacts with a hydrogen generating material piece to generate hydrogen and supplies it to the battery body, and the hydrogen generating material piece is melted with a sprayed raw material in which an additive metal and aluminum are mixed. It is formed from a sprayed film formed by blowing off the droplets generated in the process and adhering to the film-forming surface of the film-forming substrate, and the additive metal is composed of any one or more of Sn, In or Bi. , A fuel cell contained in the range of 0.1% by mass or more and 20% by mass or less with respect to 100% by mass of aluminum.
Further, the present invention is a fuel cell in which the thermal spraying raw material contains Si in a range of 0.2% by mass or more and 0.5% by mass or less with respect to 100% by mass of the aluminum.
Further, the present invention is a fuel cell in which Mg is contained in the range of 0.2% by mass or more and 2% by mass or less with respect to 100% by mass of the aluminum in the thermal spraying raw material.
Further, in the present invention, the additive metal contains Bi, and the thermal spraying raw material contains Mg in a range of 0.2% by mass or more and 2% by mass or less with respect to 100% by mass of the aluminum. The hydrogen generating material piece is a fuel cell that has been heat-treated.
Further, in the present invention, the above-mentioned reaction of a fuel cell in which a hydrogen generating material piece and water are reacted in a reaction vessel to generate hydrogen, and the generated hydrogen and oxygen are reacted to generate electricity, and power is supplied to a load. A hydrogen generation method that generates hydrogen in a container, in which a molding step of molding a sprayed raw material in which an additive metal and aluminum are mixed to obtain a sprayed material having a predetermined shape, and a molding step of melting the sprayed material to generate droplets. A spraying step of forming the molten film by blowing off the droplets and adhering them to the film-forming surface of the film-forming substrate to form a sprayed film, and after peeling the sprayed film from the film-forming surface, a desired shape is formed from the sprayed film. The additive metal has a cutting step of forming a hydrogen-generating material piece and a hydrogen-generating step of bringing the hydrogen-generating material piece and water into contact with each other in the reaction vessel to generate hydrogen by the reaction. , In or Bi, and is a hydrogen generation method containing 0.1% by mass or more and 20% by mass or less with respect to 100% by mass of aluminum.
Further, the present invention is a hydrogen generation method in which a rolling step of rolling and thinning the sprayed film is provided after the spraying step and before the cutting step.
Further, the present invention is a hydrogen generation method in which Si is contained in the range of 0.2% by mass or more and 0.5% by mass or less with respect to 100% by mass of the aluminum in the thermal spraying raw material.
Further, the present invention is a hydrogen generation method in which Mg is contained in the range of 0.2% by mass or more and 2% by mass or less with respect to 100% by mass of the aluminum in the thermal spraying raw material.
Further, in the present invention, the additive metal contains Bi, and the thermal spraying raw material contains Mg in a range of 0.2% by mass or more and 2% by mass or less with respect to 100% by mass of the aluminum, and the thermal spraying film or This is a hydrogen generation method for heat-treating the hydrogen generation material piece.
Further, in the present invention, the additive metal composed of any one or more of Sn, In or Bi is contained in the range of 0.1% by mass or more and 20% by mass or less with respect to 100% by mass of aluminum. Is a hydrogen generating material having a structure dispersed in the aluminum.
Further, the present invention is a hydrogen generating material containing Si in a range of 0.2% by mass or more and 0.5% by mass or less with respect to 100% by mass of the aluminum.
Further, the present invention is a hydrogen generating material containing Mg in a range of 0.2% by mass or more and 2% by mass or less with respect to 100% by mass of the aluminum.
Further, the present invention is a hydrogen generating material in which the additive metal contains Bi, contains Mg in a range of 0.2% by mass or more and 2% by mass or less with respect to 100% by mass of the aluminum, and is heat-treated. ..

水素発生材料を安全に保管することができる。
水素ガスを安全に発生させることができる。
必要な量の水素を発生させることができる。 The hydrogen generating material can be safely stored.
Hydrogen gas can be generated safely.
The required amount of hydrogen can be generated.

(ａ)〜(ｅ)：本発明の水素発生材料片を製造する工程を説明するための図(A)-(e): The figure for demonstrating the process of manufacturing the hydrogen generating material piece of this invention. 溶射工程を説明するための図Diagram for explaining the thermal spraying process (ａ)：水素発生装置、(ｂ)：燃料電池(a): Hydrogen generator, (b): Fuel cell

まず、水素発生材料の製造工程を説明する。
＜成形工程＞
先ず、アルミニウムに、後述する添加金属を添加してアルミニウム合金から成る溶射原料４を作成する（図１(ａ)）。 First, the manufacturing process of the hydrogen generating material will be described.
<Molding process>
First, a thermal spraying raw material 4 made of an aluminum alloy is prepared by adding an additive metal described later to aluminum (FIG. 1 (a)).

例えば、熔融されたアルミニウムに添加金属を添加して混合し、冷却して溶射原料を作成してもよいし、アルミニウムと添加金属とを加熱溶融させ、混合した後冷却して溶射原料を作成してもよい。溶射原料は例えばインゴット状である。 For example, an additive metal may be added to molten aluminum and mixed to prepare a thermal spraying raw material, or aluminum and the additive metal may be heated and melted, mixed and then cooled to prepare a thermal spraying raw material. You may. The thermal spray raw material is, for example, ingot-shaped.

次に、溶射原料を所定の形状に加工して溶射材料を得る。溶射材料を構成するアルミニウム合金は、溶射原料と同じ成分である。
図１(ｂ)の符号２は溶射原料がワイヤー形状に成形された溶射材料であり、ワイヤー形状の溶射材料２を作成する加工法としては、伸線加工、引き抜き加工、押し出し加工等の加工方法が挙げられる。 Next, the thermal spraying raw material is processed into a predetermined shape to obtain a thermal spraying material. The aluminum alloy constituting the thermal spraying material has the same components as the thermal spraying raw material.
Reference numeral 2 in FIG. 1B is a thermal spraying material in which the thermal spraying raw material is formed into a wire shape, and as a processing method for producing the thermal spraying material 2 in a wire shape, a processing method such as wire drawing, drawing, or extrusion is performed. Can be mentioned.

＜溶射工程＞
次に、図２の符号６０は、この溶射材料２を溶射処理する溶射装置である。
この溶射装置６０は、ノズル６１の内部に溶射室６３が設けられている。溶射室６３の内部には、溶射材料２が配置されており、溶射材料２の熔融物が吹き飛ばされて形成された溶滴である溶射物７３が放出される放出口６６の前面には、成膜用基板１０の成膜面２１が配置されている。成膜用基板１０は金属製又はセラミックス製の板であり、成膜面２１は、その片面である。 <Spraying process>
Next, reference numeral 60 in FIG. 2 is a thermal spraying device for thermal spraying the thermal spray material 2.
The thermal spraying device 60 is provided with a thermal spraying chamber 63 inside the nozzle 61. The thermal spray material 2 is arranged inside the thermal spray chamber 63, and is formed on the front surface of the discharge port 66 from which the thermal spray material 73, which is a droplet formed by blowing off the melt of the thermal spray material 2, is discharged. The film-forming surface 21 of the film substrate 10 is arranged. The film-forming substrate 10 is a plate made of metal or ceramics, and the film-forming surface 21 is one side thereof.

溶射室６３には着火装置が配置されており、また、溶射室６３にはガス流路６４と圧縮空気流路６５とが接続されている。
ガス流路６４はガス源に接続されており、ガス源から溶射装置６０に供給された燃焼ガスと酸素とが、ガス流路６４を通って溶射室６３の内部に流入すると、着火装置によって着火され、燃焼ガスの燃焼が開始される。 An ignition device is arranged in the thermal spraying chamber 63, and a gas flow path 64 and a compressed air flow path 65 are connected to the thermal spraying chamber 63.
The gas flow path 64 is connected to a gas source, and when the combustion gas and oxygen supplied from the gas source to the thermal spraying device 60 flow into the inside of the thermal spraying chamber 63 through the gas flow path 64, the ignition device ignites the gas flow path 64. And the combustion of the combustion gas is started.

溶射材料２は棒状体であり、その先端が溶射室６３の内部に位置するようにされている。
圧縮空気流路６５は圧縮空気源に接続されており、圧縮空気流路６５から送られる圧縮空気によってガス流路６４から送られる燃焼ガスをノズル６１の内部で燃焼させて燃焼フレームが生成されると、溶射材料２の先端は、燃焼ガスのフレーム(炎)６９と接触し、又はフレーム６９に近接した場所に位置し、燃焼ガスの燃焼によって加熱され、熔融して熔融物が生成される。 The thermal spraying material 2 is a rod-shaped body, and its tip is located inside the thermal spraying chamber 63.
The compressed air flow path 65 is connected to a compressed air source, and the combustion gas sent from the gas flow path 64 is burned inside the nozzle 61 by the compressed air sent from the compressed air flow path 65 to generate a combustion frame. The tip of the thermal spray material 2 comes into contact with the frame (flame) 69 of the combustion gas or is located near the frame 69, and is heated by the combustion of the combustion gas and melted to produce a molten material.

圧縮空気源から溶射装置６０に供給された圧縮空気は圧縮空気流路６５を流れて溶射材料２の熔融物に衝突し、熔融物を吹き飛ばして溶滴を形成する。溶滴である溶射物７３は、溶射室６３に設けられた放出口６６から溶射装置６０の外部に、圧縮空気と共に噴出され、空中を飛行する。 The compressed air supplied from the compressed air source to the thermal spraying device 60 flows through the compressed air flow path 65, collides with the melt of the thermal spray material 2, and blows off the melt to form droplets. The sprayed matter 73, which is a sprayed droplet, is ejected together with compressed air from a discharge port 66 provided in the sprayed chamber 63 to the outside of the spraying device 60, and flies in the air.

図１（ｃ）に示す通り、溶射物７３の飛行先には成膜面２１が配置されており、溶射物７３は成膜面２１に衝突すると付着する。この付着が進行すると溶射物７３の堆積が進行し、溶射物７３から成る溶射膜５が形成される（図１（ｄ））。溶射膜５の膜厚は２〜３ｍｍである。 As shown in FIG. 1 (c), the film-forming surface 21 is arranged at the flight destination of the sprayed object 73, and the sprayed object 73 adheres when it collides with the film-forming surface 21. As this adhesion progresses, the deposition of the sprayed material 73 progresses, and the sprayed film 5 made of the sprayed material 73 is formed (FIG. 1 (d)). The thermal spray film 5 has a film thickness of 2 to 3 mm.

溶射膜５は、アルミニウムに添加金属が分散された粒子同士が重なり合って互いに固着された構造になっており、添加金属が添加された熔融アルミニウムを鋳造して得られたアルミニウム合金に比べると、添加金属が均一に分散され、溶射膜５は水崩壊性を有している。
成膜面２１は平坦に形成され、鏡面に仕上げられているので、溶射膜５は成膜用基板１０から容易に剥離させることができる。 The thermal sprayed film 5 has a structure in which particles in which an additive metal is dispersed are overlapped and fixed to each other, and is added as compared with an aluminum alloy obtained by casting molten aluminum to which an additive metal is added. The metal is uniformly dispersed, and the sprayed film 5 has water disintegration property.
Since the film-forming surface 21 is formed flat and mirror-finished, the thermal spray film 5 can be easily peeled off from the film-forming substrate 10.

＜圧延工程＞
剥離させた溶射膜５を図１（ｅ）の圧延装置２０の台２３上に配置し、圧延ローラ３２によって溶射膜５を押圧しながら回転軸３３を中心として圧延ローラ３２を回転させる。溶射膜５は押圧されて薄くされて面積が大きくなる。符号６は薄くされた溶射膜を示している。 <Rolling process>
The peeled thermal spray film 5 is placed on the base 23 of the rolling apparatus 20 of FIG. 1 (e), and the rolling roller 32 is rotated around the rotation shaft 33 while pressing the thermal spray film 5 by the rolling roller 32. The thermal spray film 5 is pressed and thinned to increase the area. Reference numeral 6 indicates a thinned sprayed film.

＜切断工程＞
薄くされた溶射膜６が所望の大きさに截断されると、可搬性を有する水素発生材料片が得られる。 <Cutting process>
When the thinned sprayed film 6 is cut to a desired size, a portable hydrogen generating material piece is obtained.

＜燃料電池＞
その水素発生材料片を用いる燃料電池について説明する。
図３(ｂ)はその燃料電池１であり、水素発生装置７と電池本体８とを有している。 <Fuel cell>
A fuel cell using the hydrogen generating material piece will be described.
FIG. 3B shows the fuel cell 1, which includes a hydrogen generator 7 and a battery body 8.

先ず、水素発生装置７を説明すると、図３(ａ)を参照し、水素発生装置７は反応容器９を有しており、反応容器９の内部には水素発生材料片が配置されている。図３(ａ)の符号３は、小径の円盤状に成形された水素発生材料片を示している。
反応容器９は、開口４５と、開口４５を塞ぐ蓋４６とを有しており、蓋４６を開けると、開口４５から反応容器９の内部に水を注入できるようにされている。 First, the hydrogen generator 7 will be described. With reference to FIG. 3A, the hydrogen generator 7 has a reaction vessel 9, and a hydrogen generating material piece is arranged inside the reaction vessel 9. Reference numeral 3 in FIG. 3A indicates a hydrogen generating material piece formed into a disk shape having a small diameter.
The reaction vessel 9 has an opening 45 and a lid 46 for closing the opening 45, and when the lid 46 is opened, water can be injected into the inside of the reaction vessel 9 from the opening 45.

次に、電池本体８を説明すると、電池本体８は反応容器１１を有しており、反応容器１１の内部は板状にされた電解質１４によって燃料室１３と空気室１５とに二分されている。ここでは、電解質１４には固体電解質が用いられている。 Next, the battery body 8 will be described. The battery body 8 has a reaction vessel 11, and the inside of the reaction vessel 11 is divided into a fuel chamber 13 and an air chamber 15 by a plate-shaped electrolyte 14. .. Here, a solid electrolyte is used as the electrolyte 14.

燃料室１３側の電解質１４の片面には燃料極１６が密着して配置され、燃料室１３の内部空間は燃料極１６と接触しながら電解質１４とは非接触にされている。また、電解質１４の空気室１５側の面には空気極１７が密着して配置され、空気室１５の内部空間は空気極１７と接触しながら電解質１４とは非接触にされている。 The fuel electrode 16 is closely arranged on one side of the electrolyte 14 on the fuel chamber 13 side, and the internal space of the fuel chamber 13 is in contact with the fuel electrode 16 but not in contact with the electrolyte 14. Further, the air electrode 17 is closely arranged on the surface of the electrolyte 14 on the air chamber 15 side, and the internal space of the air chamber 15 is in contact with the air electrode 17 and is not in contact with the electrolyte 14.

ここでは、燃料極１６の電解質１４と接触した面とは反対側の面は燃料室１３の内部空間に露出されており、空気極１７の電解質１４と接触した面とは反対側の面は空気室１５の内部空間に露出されている。 Here, the surface of the fuel electrode 16 opposite to the surface in contact with the electrolyte 14 is exposed in the internal space of the fuel chamber 13, and the surface of the air electrode 17 opposite to the surface in contact with the electrolyte 14 is air. It is exposed in the internal space of the room 15.

反応容器９には水素ガス放出口１２が設けられ、燃料室１３には水素ガス導入口２７が設けられており、水素ガス放出口１２と水素ガス導入口２７とを配管２８によって接続すると、反応容器９の内部空間と燃料室１３の内部空間とが配管２８によって接続される。
開口４５から水を反応容器９の内部に投入し、次いで、水素発生材料片３を開口４５から投入し、蓋４６によって開口４５を閉じる。 The reaction vessel 9 is provided with a hydrogen gas discharge port 12, and the fuel chamber 13 is provided with a hydrogen gas introduction port 27. When the hydrogen gas discharge port 12 and the hydrogen gas introduction port 27 are connected by a pipe 28, a reaction occurs. The internal space of the container 9 and the internal space of the fuel chamber 13 are connected by a pipe 28.
Water is poured into the reaction vessel 9 through the opening 45, then the hydrogen generating material piece 3 is poured through the opening 45, and the opening 45 is closed by the lid 46.

水素発生材料片３は、Ａｌに添加金属が含有されたアルミニウム合金であり、添加金属は、Ｓｎ、Ｉｎ又はＢｉのいずれか一種又は複数種から成り、アルミニウム１００質量％に対して(以下同じ)、添加金属を０．１質量％以上２０質量％以下の範囲で含有されている。 The hydrogen generating material piece 3 is an aluminum alloy in which an additive metal is contained in Al, and the additive metal is composed of any one or more of Sn, In or Bi, and is based on 100% by mass of aluminum (the same applies hereinafter). , Additive metal is contained in the range of 0.1% by mass or more and 20% by mass or less.

水素発生材料片３は水と接触すると、水は、水素発生材料片３を構成する粒子の間に侵入し、アルミニウム合金と水とが反応して水素ガスが発生する。
Ｓｎ、Ｉｎ、Ｂｉはアルミニウム中に均一に分散されることで、アルミニウム合金が水と接触したときに、電気化学的な反応を起こし水素発生材料片３を構成するアルミニウム合金が水素を発生させながら崩壊する。 When the hydrogen generating material piece 3 comes into contact with water, the water invades between the particles constituting the hydrogen generating material piece 3, and the aluminum alloy reacts with water to generate hydrogen gas.
Sn, In, and Bi are uniformly dispersed in aluminum, so that when the aluminum alloy comes into contact with water, an electrochemical reaction occurs and the aluminum alloy constituting the hydrogen generating material piece 3 generates hydrogen. Collapse.

水素発生材料片３が全部反応するまでには所定時間を要し、その間には水素は継続して発生する。
また、水素の発生量は水素発生材料片３の量に比例しており、反応容器９の中に投入する水素発生材料片３の量によって発生する水素の量を制御することができる。
また、水素発生材料片３の反応が終了しても、新しい水素発生材料片３を反応容器９に投入することで、水素ガスの発生を再開することができる。 It takes a predetermined time for all the hydrogen generating material pieces 3 to react, and hydrogen is continuously generated during that time.
Further, the amount of hydrogen generated is proportional to the amount of the hydrogen generating material piece 3, and the amount of hydrogen generated can be controlled by the amount of the hydrogen generating material piece 3 charged into the reaction vessel 9.
Further, even if the reaction of the hydrogen generating material piece 3 is completed, the generation of hydrogen gas can be restarted by putting a new hydrogen generating material piece 3 into the reaction vessel 9.

＜発電工程＞
このように、水素発生材料片３が反応容器９の内部で水崩壊し、Ｈ2(水素ガス)を発生させると、発生したＨ2は、燃料室１３に移動する。 <Power generation process>
In this way, when the hydrogen generating material piece 3 water-collapses inside the reaction vessel 9 to generate H 2 (hydrogen gas), the generated H 2 moves to the fuel chamber 13.

燃料極１６は水素ガスを透過させ、空気極１７は酸素ガスを透過させるように構成されている。燃料室１３内に導入された水素ガスは、燃料極１６の内部に侵入する。 The fuel electrode 16 is configured to allow hydrogen gas to permeate, and the air electrode 17 is configured to allow oxygen gas to permeate. The hydrogen gas introduced into the fuel chamber 13 invades the inside of the fuel electrode 16.

空気室１５には、空気導入口２５と排出口２６とが設けられており、空気導入口２５から空気室１５の内部に空気が導入され、空気が空気極１７に接触すると、酸素ガスは空気極１７の内部に侵入する。 The air chamber 15 is provided with an air inlet 25 and an exhaust port 26. When air is introduced into the air chamber 15 from the air inlet 25 and the air comes into contact with the air electrode 17, the oxygen gas becomes air. It invades the inside of the pole 17.

燃料極１６の内部で電子が水素ガスから燃料極１６に移動して水素イオンが生成され、空気極１７の内部で電子が空気極１７から酸素ガスに移動して酸素イオンが生成される。燃料極１６と空気極１７とは、端子２４、２２に接続されており、端子２２、２４の間に負荷を接続すると、水素ガスから放出された電子は燃料極１６から負荷を通って空気極１７へ移動し、その結果、負荷に電流が流れる。 Inside the fuel pole 16, electrons move from the hydrogen gas to the fuel pole 16 to generate hydrogen ions, and inside the air pole 17, electrons move from the air pole 17 to the oxygen gas to generate oxygen ions. The fuel pole 16 and the air pole 17 are connected to the terminals 24 and 22, and when a load is connected between the terminals 22 and 24, the electrons released from the hydrogen gas pass through the load from the fuel pole 16 and the air pole. It moves to 17, and as a result, current flows through the load.

電解質１４は、水素イオン又は酸素イオンが通過する材料で構成されており、電解質１４内を水素イオンが移動すると、電解質１４と空気極１７とが接触する場所で水が生成され、電解質１４の内部を酸素イオンが移動すると、電解質１４と燃料極１６とが接触する場所で水が生成される。 The electrolyte 14 is composed of a material through which hydrogen ions or oxygen ions pass, and when hydrogen ions move in the electrolyte 14, water is generated at a place where the electrolyte 14 and the air electrode 17 come into contact with each other, and the inside of the electrolyte 14 is generated. When oxygen ions move, water is generated at the place where the electrolyte 14 and the fuel electrode 16 come into contact with each other.

ここでは電解質１４には水素イオンが移動する材料が用いられており、電解質１４と空気極１７とが接触する場所で生成された水は空気極１７を通過して空気室１５の内部空間に放出され、排出口２６から大気中に放出される。 Here, a material in which hydrogen ions move is used for the electrolyte 14, and water generated at a place where the electrolyte 14 and the air electrode 17 come into contact with each other passes through the air electrode 17 and is discharged into the internal space of the air chamber 15. It is released into the air from the discharge port 26.

反応容器９の内部で水素発生材料片３が水素を発生させている間は、水素イオンと酸素イオンとが生成され、水素イオンと酸素イオンとが化合して水が生成される。その間は燃料電池１は発電して負荷に電力を供給しており、水素発生材料片３の水崩壊が終了すると、発電を終了させてもよいし、反応容器９に水素発生材料片３を追加して発電を継続させてもよい。 While the hydrogen generating material piece 3 is generating hydrogen inside the reaction vessel 9, hydrogen ions and oxygen ions are generated, and the hydrogen ions and oxygen ions combine to generate water. During that time, the fuel cell 1 generates electric power and supplies electric power to the load. When the water decay of the hydrogen generating material piece 3 is completed, the power generation may be terminated, or the hydrogen generating material piece 3 is added to the reaction vessel 9. And the power generation may be continued.

なお、水素発生材料片３の作成方法として、アルミニウムに添加金属を添加して混合するだけでは水崩壊性を発現させることはできず、一旦アルミニウムと添加金属とを混合して得られたアルミニウム合金から、溶射材料を成形し、溶射方法によって熔融・溶射・固化させた後、所定形状に成形すると、水崩壊性を有する水素発生材料片３を得ることができる。 As a method for producing the hydrogen generating material piece 3, it is not possible to exhibit water disintegration only by adding an additive metal to aluminum and mixing it, and an aluminum alloy obtained by once mixing aluminum and the additive metal. From the above, a sprayed material is molded, melted, sprayed, and solidified by a spraying method, and then molded into a predetermined shape to obtain a hydrogen generating material piece 3 having water disintegration property.

添加金属に加え、アルミニウム合金に０．５質量％以下の範囲でＣｅを添加しておくと、水崩壊性が安定して発現するようになる。また、添加金属に加え、アルミニウム合金にＴｉを添加するとアルミニウムの再結晶化温度が上昇するので、溶射によって溶射膜を形成する際に、添加金属の析出を防止することができる。Ｔｉは、Ａｌ１００質量％に対して０．１３質量％以上４質量％以下の含有率で含有させるとよい。 When Ce is added to the aluminum alloy in the range of 0.5% by mass or less in addition to the added metal, the water disintegration property is stably exhibited. Further, when Ti is added to the aluminum alloy in addition to the added metal, the recrystallization temperature of aluminum rises, so that precipitation of the added metal can be prevented when the sprayed film is formed by thermal spraying. Ti is preferably contained at a content of 0.13% by mass or more and 4% by mass or less with respect to 100% by mass of Al.

本発明の水素発生材料片３の一部は、特に空気を遮断しなくても長期間の保存ができるように調整可能である。 A part of the hydrogen generating material piece 3 of the present invention can be adjusted so that it can be stored for a long period of time without particularly shutting off the air.

アルミニウム１００質量％に対してＳｉを０．２質量％以上０．５質量％以下の範囲で含有させると、水崩壊性を維持したまま、空気中の水分による水崩壊を防止することができる。 When Si is contained in the range of 0.2% by mass or more and 0.5% by mass or less with respect to 100% by mass of aluminum, water collapse due to moisture in the air can be prevented while maintaining water disintegration property.

Ｓｉを添加して空気中の水分による水崩壊を防止した本発明の水素発生材料片３を、５年間大気に接触する状態で保管したが、変化はなかった。さらにその水素発生材料片３を水の中に投入すると、直ちに反応が始まり水素が発生した。 The hydrogen generating material piece 3 of the present invention, in which Si was added to prevent water collapse due to moisture in the air, was stored in contact with the atmosphere for 5 years, but there was no change. Further, when the hydrogen generating material piece 3 was put into water, the reaction started immediately and hydrogen was generated.

また、アルミニウム１００質量％に対してＭｇを０．２質量％以上含有させても、空気中の水分による水崩壊を防止することができる。但し、２質量％を超えると加工性が悪くなるのでＭｇは、０．２質量％以上２質量％以下含有させることが好ましい。 Further, even if 0.2% by mass or more of Mg is contained with respect to 100% by mass of aluminum, water collapse due to moisture in the air can be prevented. However, if it exceeds 2% by mass, the workability deteriorates, so it is preferable to contain Mg in an amount of 0.2% by mass or more and 2% by mass or less.

特に、添加金属としてＢｉを含有する場合に、更にＭｇを含有させると、溶射膜が形成された後２００℃以上３００℃以下の温度に昇温される熱処理が行われると水又は温水(「温水」は６０℃以上１００℃以下に昇温した水とする。)で水崩壊するが、熱処理が行われない場合には、水又は温水では水崩壊が発生しなくなる。 In particular, when Bi is contained as an additive metal and Mg is further contained, water or hot water (“warm water”) is subjected to heat treatment in which the temperature is raised to 200 ° C. or higher and 300 ° C. or lower after the thermal spray film is formed. "Is water that has been heated to 60 ° C. or higher and 100 ° C. or lower.) However, if heat treatment is not performed, water collapse does not occur in water or warm water.

熱処理は溶射膜５に行っても良いし、水素発生材料片３に行っても良い。圧延ローラ３２で溶射膜５を薄くする際に、圧延ローラ３２を加熱し、押圧する溶射膜５を２００℃以上３００℃以下の温度に加熱するようにしてもよい。 The heat treatment may be performed on the sprayed film 5 or the hydrogen generating material piece 3. When the thermal spray film 5 is thinned by the rolling roller 32, the rolling roller 32 may be heated and the thermal spray film 5 to be pressed may be heated to a temperature of 200 ° C. or higher and 300 ° C. or lower.

従って、溶射膜５の形成後、熱処理を行わないで水素発生材料片３を作成し、使用の直前に熱処理を行うようにすれば、保管中に水崩壊が発生しない水素発生材料片３を得ることができる。 Therefore, if the hydrogen generating material piece 3 is prepared without heat treatment after the thermal spray film 5 is formed and the heat treatment is performed immediately before use, the hydrogen generating material piece 3 that does not cause water decay during storage can be obtained. be able to.

このように本発明の水素発生材料片３は、水との反応性を調整することができるが、反応性を高くしたい場合や、湿度の高い環境でより長期の保管する場合、浸水などによる反応を防止する場合には、水素発生材料片３を樹脂フィルムで封止し、水素発生材料片３と大気や水分とが接触しないようにしてもよいし、水素発生材料片３を容器に入れ、容器に蓋をして水素発生材料片３と大気や水分とが接触しないようにしてもよい。 As described above, the hydrogen generating material piece 3 of the present invention can adjust the reactivity with water, but when it is desired to increase the reactivity or when it is stored for a longer period of time in a humid environment, the reaction due to water immersion or the like. In the case of preventing the above, the hydrogen generating material piece 3 may be sealed with a resin film to prevent the hydrogen generating material piece 3 from coming into contact with the atmosphere or moisture, or the hydrogen generating material piece 3 may be placed in a container. The container may be covered to prevent the hydrogen generating material piece 3 from coming into contact with the air or moisture.

このように本発明の水素発生材料片３は、アルカリ金属のように特別な保管手段を必要とすることなく長期の保管が可能なので、長期保管が望まれる緊急災害用の燃料電池の水素発生材料として好適である。
さらに、水としては、水道水の他、海水、湖水、河川の水、雨水等を使用でき、水が主成分であれば種類・純度を問わないので、災害時に好適である。 As described above, the hydrogen generating material piece 3 of the present invention can be stored for a long period of time without requiring a special storage means like an alkali metal. Therefore, a hydrogen generating material for an emergency disaster fuel cell for which long-term storage is desired. Is suitable as.
Further, as water, in addition to tap water, seawater, lake water, river water, rainwater, etc. can be used, and as long as water is the main component, the type and purity are not limited, so that it is suitable in the event of a disaster.

特に燃料電池は回転機構等がないためメンテナンス無しで長期の保管が可能で、軽量で、かつ、単独で発電可能なため、遠隔地や離島での緊急発電機として期待される。さらに、本発明の水素発生材料片３を備蓄すれば、安全に長期間の保管が可能である。 In particular, fuel cells do not have a rotating mechanism, so they can be stored for a long time without maintenance, are lightweight, and can generate electricity independently, so they are expected to be emergency generators in remote areas and remote islands. Further, if the hydrogen generating material piece 3 of the present invention is stored, it can be safely stored for a long period of time.

１３……燃料室
１４……電解質
１５……空気室
１６……燃料極
１７……空気極
２５……空気導入口
２６……排出口
２７……水素ガス導入口
２８……配管
13 …… Fuel chamber 14 …… Electrolyte 15 …… Air chamber 16 …… Fuel pole 17 …… Air pole 25 …… Air inlet 26 …… Discharge port 27 …… Hydrogen gas inlet 28 …… Piping

Claims (10)

水素発生材料片と水とを反応させて水素を生成し、生成された水素と酸素を反応させて発電し、負荷に電力を供給する燃料電池の水素を発生させる燃料電池の前記水素発生材料片を製造する水素発生材料製造方法であって、
添加金属とアルミニウムとが混合された溶射原料を成形して所定形状の溶射材料を得る成形工程と、
前記溶射材料を熔融させて熔融物の溶滴を吹き飛ばして成膜用基板の成膜面に付着させて溶射膜を形成する溶射工程と、
前記溶射膜を前記成膜面から剥離させ、前記溶射膜から所望形状の水素発生材料片を形成する片形成工程と、
を有し、
前記添加金属は、Ｓｎ、Ｉｎ又はＢｉのいずれか一種又は複数種から成り、アルミニウム１００質量％に対して０．１質量％以上２０質量％以下の範囲で含有させる水素発生材料製造方法。 The hydrogen-generating material piece of a fuel cell that generates hydrogen by reacting a hydrogen-generating material piece with water to generate hydrogen, and reacting the generated hydrogen with oxygen to generate electricity and supply electric power to a load. This is a method for producing hydrogen-generating materials.
A molding process in which a thermal spraying raw material in which an additive metal and aluminum are mixed is molded to obtain a thermal spraying material having a predetermined shape.
A thermal spraying step of melting the thermal spray material to blow off droplets of the melt and adhering it to the film-forming surface of the film-forming substrate to form a thermal spray film.
A piece forming step of peeling the sprayed film from the film-forming surface to form a hydrogen generating material piece having a desired shape from the sprayed film.
Have,
A method for producing a hydrogen generating material, wherein the additive metal is composed of any one or a plurality of Sn, In or Bi, and is contained in a range of 0.1% by mass or more and 20% by mass or less with respect to 100% by mass of aluminum. 前記溶射工程の後、前記溶射膜を圧延して薄くする圧延工程が設けられた請求項１記載の水素発生材料製造方法。 The method for producing a hydrogen generating material according to claim 1, wherein after the thermal spraying step, a rolling step of rolling and thinning the thermal sprayed film is provided. 前記溶射原料には前記アルミニウム１００質量％に対してＳｉを０．２質量％ 以上０．５質量％以下の範囲で含有させた、請求項１又は請求項２のいずれか１項記載の水素発生材料製造方法。 The hydrogen generation according to any one of claims 1 or 2, wherein the thermal spraying raw material contains Si in a range of 0.2% by mass or more and 0.5% by mass or less with respect to 100% by mass of the aluminum. Material manufacturing method. 前記溶射原料には前記アルミニウム１００質量％に対して、Ｍｇを０．２質量％以上２質量％以下の範囲で含有させた、請求項１乃至請求項３のいずれか１項記載の水素発生材料製造方法。 The hydrogen generating material according to any one of claims 1 to 3, wherein the thermal spraying raw material contains Mg in a range of 0.2% by mass or more and 2% by mass or less with respect to 100% by mass of the aluminum. Production method. 前記添加金属はＢｉを含有し、前記溶射原料には前記アルミニウム１００質量％ に対して０．２質量％以上２質量％以下の範囲でＭｇを含有させ、前記溶射膜又は前記水素発生材料片の少なくとも一方を熱処理する請求項１乃至請求項３のいずれか１ 項記載の水素発生材料製造方法。 The additive metal contains Bi, and the thermal spraying raw material contains Mg in a range of 0.2% by mass or more and 2% by mass or less with respect to 100% by mass of the aluminum, and the thermal spray film or the hydrogen generating material piece. The method for producing a hydrogen generating material according to any one of claims 1 to 3, wherein at least one of them is heat-treated. 水素発生材料片と水とを反応容器内で反応させて水素を生成し、生成された水素と酸素を反応させて発電し、負荷に電力を供給する燃料電池の前記反応容器内で水素を発生させる水素発生方法であって、
添加金属とアルミニウムとが混合された溶射原料を成形して所定形状の溶射材料を得る成形工程と、
前記溶射材料を熔融させて溶滴を生成し、前記溶滴を吹き飛ばして成膜用基板の成膜面に付着させて溶射膜を形成する溶射工程と、
前記溶射膜を前記成膜面から剥離させた後、前記溶射膜から所望形状の水素発生材料片を形成する切断工程と、
前記水素発生材料片と水とを前記反応容器内で接触させ、反応によって水素を発生させる水素発生工程と、を有し、
前記添加金属は、Ｓｎ、Ｉｎ又はＢｉのいずれか一種又は複数種から成り、アルミニウム１００質量％に対して０．１質量％以上２０質量％以下の範囲で含有させる水素発生方法。 Hydrogen generation Material pieces and water are reacted in a reaction vessel to generate hydrogen, and the generated hydrogen reacts with oxygen to generate electricity, and hydrogen is generated in the reaction vessel of a fuel cell that supplies electric power to a load. It is a hydrogen generation method to make
A molding process in which a thermal spraying raw material in which an additive metal and aluminum are mixed is molded to obtain a thermal spraying material having a predetermined shape.
A thermal spraying step in which the thermal spray material is melted to generate droplets, and the droplets are blown off and adhered to the film-forming surface of the film-forming substrate to form a thermal spray film.
A cutting step of forming a hydrogen generating material piece having a desired shape from the sprayed film after peeling the sprayed film from the film-forming surface.
It has a hydrogen generation step of bringing the hydrogen generating material piece and water into contact with each other in the reaction vessel to generate hydrogen by the reaction.
A hydrogen generation method in which the additive metal is composed of any one or more of Sn, In or Bi, and is contained in the range of 0.1% by mass or more and 20% by mass or less with respect to 100% by mass of aluminum. 前記溶射工程の後、前記切断工程の前に、前記溶射膜を圧延して薄くする圧延工程が設けられた請求項６記載の水素発生方法。 The hydrogen generation method according to claim 6 , wherein a rolling step of rolling and thinning the thermal spray film is provided after the thermal spraying step and before the cutting step. 前記溶射原料には前記アルミニウム１００質量％に対してＳｉを０．２質量％以上０．５質量％以下の範囲で含有させた、請求項６又は請求項７のいずれか１項記載の水素発生方法。 The hydrogen generation according to any one of claims 6 or 7 , wherein the thermal spraying raw material contains Si in a range of 0.2% by mass or more and 0.5% by mass or less with respect to 100% by mass of the aluminum. Method. 前記溶射原料には前記アルミニウム１００質量％に対して、Ｍｇを０．２質量％以上２質量％以下の範囲で含有させた、請求項６乃至請求項８のいずれか１項記載の水素発生方法。 The hydrogen generation method according to any one of claims 6 to 8 , wherein the thermal spraying raw material contains Mg in a range of 0.2% by mass or more and 2% by mass or less with respect to 100% by mass of the aluminum. .. 前記添加金属はＢｉを含有し、前記溶射原料には前記アルミニウム１００質量％に対して０．２質量％以上２質量％以下の範囲でＭｇを含有させ、前記溶射膜又は前記水素発生材料片を熱処理する請求項６乃至請求項８のいずれか１項記載の水素発生方法。 The additive metal contains Bi, and the thermal spraying raw material contains Mg in a range of 0.2% by mass or more and 2% by mass or less with respect to 100% by mass of the aluminum, and the thermal spray film or the hydrogen generating material piece is used. The hydrogen generation method according to any one of claims 6 to 8 , wherein the heat treatment is performed.
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